Antioxidant or age-resister



' 35 formula Patented June '9, 1931 a UNI ED sTA' Tesf PATEN OFFICE ALB RrMoLIFroR-n on AKRON, OHIO, AssmNonmo THE GOODYEAR TIRE & RUB

2 BER COMPANY, OF AKRON, OHIO, A. CORPORATION OFOHIO ANTIOXIDANT on aerrfnnsrsrnn No Drawing.

1 This invention relates to the manufacture; of rubber compounds' anditthas particular relation'to the manufacture of compounds which ofier an exceptionally highdegree of;

5 resistance to the action OfSllClllflgQIlClBS as oxygen and-light, which normally cause premature aging andvdecay thereof. 7

An object of the invention is to provide a novel method of manufacturing age-resist- K ing rubber compounds which involves the use of abundantand relatively inexpensive materials for which'there is but little unseat;

the, present time. p

'Heretofore, in

decay of rubber goods under the action of air. and sunlight; In order to reduce these losses,it has been proposed to introduce cer-.

tain compounds, such as hydroquinone, di'-,,

,This invention consists in the discovery that: :acenaphthene; a; compound having the efieetive for this purpose: a amino acenaph the industries much loss has been occasioned;,-'because ofgpremature.

from which they: f

" Application filed January 16, 1930;} Serial no. 421,231.

thene; 3-beta-naphthyl "amido acenaph I thene; 3,-a"lpha' 'naphthyl amino acenaphthene; 3-hy'droxy a'cenaphthene diamino 'acenaphthen'e; such aldehyde derivatives of 3-amino, acenaphthene as the following: formaldehyde, acetaldeh'yde, butyraldehyde' and crotonaldehyde; symmetricalethylene di-acenaphthene; 2-4-diamino phenyl 3- amino acenaphthene 3-formyl amino ace naphthene; and di acenaphthene amine. I

The 3-amino "'acenaphthene "compound;

thene by any convenient method, for example;

by the use; of iron filings and dilute hydrochloric acid; Such reductions arewell known to chemists and need not bediscussed in 0 phenylamine and certain aldehydearomatid detail; I

In the preparation of 3-beta naphthyl whichatthepresent time is'one of the most practicable members of the series from a amino acenaphthene, '3-amino acenaphthene is intermixed molar ratio with beta naphthol vand subjected to heat and pressure in an -autoclave.- The latter treatment "should be continued'for a period of approximately 6 to'8hours and 'at a temperature ranging from 260 to" 290 C. Theresultanttproduc't is-obtained a-s a somewhat pasty mass by washing the crude material as it is obtained,

from the autoclave "witha dilute solution of free or unreactedfnaphthol. we Purification may be rendered somewhat; more complete by further-Washing the partially purifiedzmaterial with hot water. A similar method may thol :for' beta-naphthol. I1 I However, under present conditions the alpha compoundis less ra'cticable from commercial standpoint clause of the-relatively expensive character of alphanaphthet' 5 r Y Although the antioxidants discussed may be employed for the preparation of the alpha 1 naphthyl amine compound, the only difi'eri ence be ng in'the substitutionof:alpha-naphbe employed in substantially any of the standard rubber formulae, the following is an example of such formula in which they have been found to be particularly effective.

Parts Acetone extracted rubber 100 Zinc oxide 5 Sulphur 3 Stearic acid 1. 5 Hexamethylene tetramine 1 Antioxidantf l; .LQLQAQLL 1 as n e. r g na W ght ther o after which. hey werep aced ina-n oxygen om and s bjec d t t e ac o o o ygen under a Pressure t P unds. per qu e nch an at a temp t eo 0 or a p riod. o six ay The mples ere ea Weighed a e n me in r er to a ertain he pe t g of y n bs bed, a te hit t ey wer s j c e to the ame. Phy ical tests co ducted, p the us-s d amp es.- T e. res s se t st e bu ted follows:

Cure Loadiln kzs/cmlat v Percent Tim in 5007 1007 gigging. iii 8 pera- L T6886 mlhs. are along. along. Husk ami at ch en '35 285 a '52] 150" 50 285' 24 83' 141. 790 10 285 as 130 17a 5 750 can.

35 285 a2- 78 7/ 13a. s00 .11 so 285 -30 112 15.6 760' .18 T 3E5 4 160 t I 0' 8.-h mnl fi u mido acencpmhene.

QBIGINnI,

=53 zss -10 21 as, 915 i V 60, 13; 1 43 121 i 860 19 64 4 AGED e 38 "ad 69 so 285' 1s 00 5 108 i 806 .ii 70 as; 2a 8a 124 7 70; y .13

naphthene or 3-beta naphthylamido acenaphthene resist, to a remarkable degree, the action of oxygen even under the relatively severe conditions existing in the above test.

Under similar conditions, samples identical with those described above, except for the omission of any antioxidant are reduced to resinous masses substantially devoid of elasticity and tensile strength and worthless for all practical purposes.

The compounds are not only desirable because of the high antioxidant properties possessed thereby, but also because they may be prepared from acenaphthene, a coal tar by: product for which there is but little or no market at the present time and which may therefore be obtained in abundance and at slight expense. Transformation of the original: or basic materials to the desired amino derivatives may be accomplished with comparative ease. Accordingly, the cost of the antioxidants is relatively slight as compared with that ofmany materials now ofiered on the market. The materials are also ractically odorless and non-toxic, and for tIi at reason, their use in rubber compounds does not entail any unusual precautions in the handling thereof. I

Although I have described-in detail only the preferred forms of the invention,it will be apparent to those skilled in the art that it is not so limited, but that various modifications may be made therein without departing from the spirit of the invention or from the'scope of the appended claims,

' What I claim is:

1. A method of preserving rubber which comprises subjecting it to vulcanization in the presence of an amino derivative of acena hthene.

2. method of preserving rubber which the presence of 3-amino acenaphthene.

3. A methodv of preserving'rubber which comprises'subjecting it to vulcanizationin the presence of 3-beta-naphthylamido amnaphtheneQ 4. A method of preserving rubber which comprises subjecting it to vulcanization in the presence of a pro-amino derivative of acenaphthene.

5. method of preserving rubber which comprlses sub'ecting it to vulcanization in the presence 0 a reaction product of 3-aminoacenaphthene and naphthol.

6. method-of preserving rubber which comprises subjecting it to vulcanization in the presence of a reaction product of 3- amino acenaphthene and beta-naphthol.

7, A rubber product that has been vulin the presence of an amino. derivat ve. of c naphthene.

8 rubber product that has been vulcanwed in the presence of a 3-amino of acenaphhese R, whereR is attached to the naphthalene nucleus and is selected fromthe groupconsisting of hydrogen,OH amino, hydrocarbon substituted amino groups naphthyla-mine o groups, and residues obtained by condensing amino acenaphthene with an open chain aldehyde.

13. A method of preserving rubber which comprises subjectin it to cure in the presence of a material inclu ing the following group:

14. A rubber product that has been Vulcan: ized in the presence of a material including the following group:

In witness whereof, I have hereunto signed my name. I Signed at Akron, in the county of Summit and State of Ohio, U. S.; A., this 14th day of January, 1930.

ALBERT M. CLIFFORD.

Certificate of Correction Patent No. 1,809,7 99. Granted June 9, 1931, to ALBERT M. CLIFFORD It is hereby certified that error'appears in the printed specification of the abovenufnbered patent requiring correction as follows: Page 2, line 115, claim 4, for the compound Word pre-amino read 3-amz'n0; page 3, between lines 11 to 15, claim 12,

strike out the formula and insert instead same claim, line 16, strike out the letter and comma Rf; line 18, after the character OH insert a comma, and line 19, insert a comma after groups; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 12th day of October, A. D1931.

[SEAL] M. J. MOORE, Acting Commissioner 0 f Patents. 

